Process for the production of halogenated malonates

ABSTRACT

THE PROCESS OF REACTING METHYLENEDIPHOSPHONATE ESTERS (C7-C22), MALONATE ESTRS (C4-C22), OR PHOSPHONOACETATE ESTERS (C8-C22) WITH HYPOHALITE IONS IN AN AQUEOUS REACTION MEDIA COMPRISING A WATER MISCIBLE ORGANIC SOLVENT; MONO- AND DIHALOGENATED METHYLENEDIPHOSPHONATE ESTERS (C9-C22); MONO- AND DIHALOGENATED MALONATE ESTERS (C4-C22); AND MONO- AND DIHALOGENATED PHOSPHONOACETATE ESTERS (C8-C22).

United States Patent 3,790,622 PROCESS FOR THE PRODUCTION OF HALOGENATEDMALONATES Denzel Allan Nicholson, Springfield, Ohio, assignor to TheProcter & Gamble Company, Cincinnati, Ohio No Drawing. Originalapplication Oct. 25, 1968, Ser. No.

770,860, now Patent No. 3,662,039. Divided and this application Dec. 27,1971, Ser. No. 212,625

Int. Cl. C07c 69/62 US. Cl. 260-48-5 H 8 Claims ABSTRACT OF THEDISCLOSURE The process of reacting methylenediphosphonate esters (C C-malonate esters (C -C or phosphonoacetate esters (C C with hypohaliteions in an aqueous reaction media comprising a water miscible organicsolvent; monoand dihalogenated methylenediphosphonate esters (Cg- 22);monoand dihalogenated malonate esters (C -C and monoand dihalogenatedphosphonoacetate esters (C -C This application is a division ofcopending application Ser. No. 770,860 filed Oct. 25, 1968, now US. Pat.3,662,039.

BACKGROUND OF THE INVENTION (1) Field of the invention This inventionrelates to a process for preparing certain monoand dihalogenatedmethylenediphosphonate esters, molonate esters and phosphonoacetateesters which contain one or two chlorine, bromine or iodine atomsattached to a methylene group which connects two moieties selected fromthe group consisting of phosphonate ester and carboxylate ester moietiesand to certain of these dihalogenated methylenediphosphonate esters,malonate esters and phosphonoacetate esters which are useful as extremepressure additives and anti-Wear additives in lubricant compositions.

(2) Prior art The US. application of Quirnby et al. Ser. No. 587,417,filed Oct. 18, 1966, and now abandoned, presents a practical process forthe production of halogenated tetraalkyl methylenediphosphonates whereinthe alkyl groups contain from about 3 to about 8 carbon atoms. The US.application of Curry, Ser. No. 717,999, filed Apr. 1, 1968, and nowabandoned, presents a practical process for the production ofhalogenated tetraalkyl methylenediphosphonates wherein the alkyl radicalcontains from 1 to 2 carbon atoms. Neither of the processes disclosed inthe above applications is suitable for preparing halogenatedmethylenediphosphonate esters, phosphonoacetate esters or malonateesters where the alcohol portion of the esters contains at least 7carbon atoms in the case of the methylenediphosphonates, at least 4carbon atoms in the case of the malonates and at least 8 carbon atoms inthe case of the phosphonoacetates. These relatively long chain alkyl andaryl esters are too insoluble in aqueous reaction media to permit thehalogenation reaction to proceed.

THE INVENTION This invention relates to the process for preparinghalogenated methylenediphosphonate esters, malonate esters andphosphonoacetate esters which are useful as extreme pressure additivesin lubricant compositions and as anti- Wear additives in lubricantcompositions; comprising the steps of reacting a compound selected fromthe group consisting of: (l) methylene-diphosphonates having the formulaR PO CH PO R wherein each R is selected from the group consisting ofalkyl, aryl, alkaryl, aralkyl, haloalkyl, haloaryl, haloalkaryl,haloaralkyl, alkenyl, halo- 7 Patented Feb. 5, 1974 alkenyl, andnitroaryl radicals containing from 7 to about 22 carbon atoms; (2)malonates having the formula ROOCCH COOR' wherein each R is selectedfrom the group consisting of alkyl, alkenyl, aryl, aralkyl, alkaryl,haloalkyl, haloalkenyl, haloaryl, haloalkyl, haloaralkyl, and nitroarylradicals containing from 4 to about 22 carbon atoms; and (3)phosphonoacetates having the formula R PO CH COOR wherein each R isselected from the group consisting of alkyl, alkenyl, aryl, alkaryl,aralkyl, haloalkyl, haloalkenyl, haloaryl, haloalkaryl, haloaralkyl andnitroaryl radicals containing from 8 to about 22 carbon atoms with ahypohalite ion selected from the group consisting of OCl-, OBr" and 01-,the

molar proportions of the reactant being selected so that there are fromabout 0.75 to about 6 moles of said hypohalite ion for each mole of saidmethylenediphospho- DETAILED DISCLOSURE The present invention isvaluable in that the reactant and the reaction conditions mentionedabove can be adjusted as shown hereinafter to produce unexpectedly highyields of the monoand dihalo derivatives of methylenediphosphonates,malonates and the phosphonoacetates containing relatively bighydrocarbyl groups.

- The reaction system is a fairly complex one, but by adhering to theconditions set forth above and more fully explained in the followingdiscussion, high yields of any of the desired monoand dihalogenatedmethylenediphosphonate esters, monoand dihalogenated malonate esters andmonoand dihalogenated phosphonoacetate esters can be obtained.

The embodiment of this invention according to which a mon'ohalo compoundis prepared is illustrated by the following equations:

(III) H o mirmomooon ox nl poaoxnooom 011- In the above equation OX-represents a hypohalite ion with X being a halogen selected from thegroup consisting of chlorine, bromine and iodine atoms; S is an inert,water-miscible organic solvent; R is selected from the group consistingof alkyl, aryl, alkaryl, aralkyl, haloalkyl, haloaryl, haloalkaryl,haloaralkyl, alkenyl haloalkenyl, and nitroaryl radicals containing from7 to about 22 carbon atoms; R is selected from the group consisting ofalkyl, alkenyl, aralkyl, aryl, aralkyl, haloalkyl, haloalkenyl,haloaryl, haloalkaryl, haloaralkyl and nitroaryl radicals containingfrom 4 to about 22 carbon atoms; and R is selected from the groupconsisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, haloalkyl,haloalkenyl, haloaryl, haloalkaryl, haloaralkyl and nitroaryl radicalscontaining from 8 to about 22 carbon atoms.

For purposes of understanding the present invention the hypohalitereactant is depicted simply as OX1 rather than as an inorganichypohalite compound. It is to be understood that the essential reactionmoiety is the hypohalite ion. It.can either be introduced as aninorganic hypohalite such as NaOBr, NaOCl, NaOI or other equivalentalkali metal or alkaline earth metal form. Alternatively, the hypohaliteion can be generated in situ by means described below.

It has been discovered that surprisingly high yields of monohalogenatedproduct can be obtained using from about 0.75 to about 1.1 moles ofhypohalite to 1 mole of methylenediphosphouate, malonate, orphosphonoacetate. It is preferred for maximum yields that from 0.95 toabout 1.1 moles of hypohalite ion to 1 mole of eithermethylenediphosphonate, malonate or phosphonoacetate be employed. It isimportant that no more than about 1.1 moles of hypohalite per mole ofmeth 1enediphosphonate, malonate or phosphonoacetate be present in theabove reaction. In order to prepare high yields of a monohalogenatedcompound a larger portion of hypohalite ion tends to carry the reactionon to form the dihalo methylenediphosphonates, malonates orphosphonoacetates as explained below. The reactions of Equations I, H,and III can be terminated :as discussed hereinafter, producingsurprisingly high yields of monohalomethylenediphosphonates malonates,or phosphonoacetates.

According to a further embodiment of this invention, the above reactioncan be allowed to continue producing the corresponding dihalomethylenediphosphonates, malonates or phosphonoacetates. In thisembodiment of the invention, the hypohalite ion reacts with the monohaloreaction product of Equations I, II and III to produce the correspondingdihalo methylenediphosphonoates, malonates or phosphonoacetates. Toprovide sufficient hypohalite ion to form dihalo ester compounds a largeexcess of hypohalite ion can be used. It has been discovered that thehighest yield of dihalo methylenediphosphonates, malonates orphosphonoacetates is obtained by using from about 2 to about 6 moles ofhypohalite ion per 1 mole of methylenediphosphonate, malonate orphosphonoacetate. It is preferred that from 2.05 to about 2.1 moles ofhypohalite ion be used per 1 mole of methylenediphosphonate, malonate orphosphonoacetate in the foregoing reactions to favor formation of thedihalo methylenediphosphonates, malonates, or phosphonoacetates.

The dihalogenation embodiment of the present inven- ,-tion is more fullyillustrated in the following equations wherein all terms are as definedin Equations I, H and III. Equation IV can be considered in conjunctionwith Equation I above in which the R PO CXHPO R starting material isthought of as the reaction product of Equation '1; Equation V can beconsidered in conjunction with Equation 11 above in which the ROOCCXHCOOR starting material is thought of as the reaction product ofEquation II; and Equation VI can be considered in conjunction withEquation HI above in which the starting material is thought of as thereaction product of Equation III.

H O R OOGGXHCOOR OK- R OOCCXzCOOR OH- H20 na roaoxuooonuox- T R2 1oaoxiooon OH- The preparation of dihalo esters can also proceedaccording to Equations IV, V and VI by beginning with monohalomethylenediphosphonates, malonates, or phosphonoacetates obtained fromany source, i.e., from Equations I, II and III or from any othersuitable reaction. In this latter event highest yields of dihalomethylenediphosphonates, malonates or phosphonoacetates are obtainedfrom using from about 1 to about 3 moles of hypohalite ion per 1 mole ofmonohalo methylenediphosphonate, malonate or phosphonoacetate andpreferably from about 1.0 to about 1.1 moles of hypohalite ion per 1mole of monohalo methylene diphosphonate, malonate or phosphonoacetatein the foregoing reactions IV-V'I. It will be understood that with thisapproach it is possible for the two Xs to be different.

The water miscible organic solvents of this invention include: alcoholscontaining from 1 to 3 hydroxy groups and from 1 to 6 carbon atoms suchas methanol, ethanol, propanol, isopropanol, butanol, isobutanol,glycerine, ethylene glycol, propylene glycol and the like; ethers(including cyclic ethers) containing from 2 to about 8 carbon atoms suchas ethylene glycol diethyl ether, butyl Cellosolve, tetrahydrofuran,1,4-dioxane, ethylene glycol dimethyl ether, propasol B, and the like;and lcetones containing from 3 to about 5 carbon atoms includingacetone, propyl methyl ketone, methyl ethyl ketone and the like.

It is preferred to keep electrolytes out of the reaction mixture sincethe electrolyte tends to keep the very waterinsolublemethylenediphosphonate, malonate and phosphonoacetate reactants fromdissolving sufiiciently in the aqueous reaction mixture to permit thehalogenation of these reactants.

The reactions set forth in Equations I-VI must be conducted above a pHof 7 at a temperature of from about 0 C. to about 75 C. These reactionstake from about 1 minute to about 2 hours, depending upon the rate ofaddition of reactant, the temperature and general reaction conditions.In the preferred embodiment of the present invention the hypohalite isadded slowly to a stirred mixture of the aqueous phase which containsthe water-miscible solvent and the insoluble methylenediphosphonate,malonate or phosphonoacetate reactant. Vigorous stirring breaks theorganic phase into tiny discrete globules intermixed with the aqueousphase. This agitation of the mixture is continued while the hypohaliteis added to the reaction mixture.

It is important in directing the process of the present invention towardthe monohalo product (Equations I, II and III) that the hypohalite beadded to the methylenediphosphonate, malonate or phosphonoacetate inorder to minimize any excessive hypohalite present during the reaction.While the foregoing represents the preferred method of adding reactantsin the process of the present invention, the hypohalite can be generatedin the aqueous phase subsequent to the addition of themethylenediphosphonate, malonate or phosphonoacetate, or themethylenediphosphonate, malonate or phosphonoacetate can be addedrapidly to the hypohalite. The reactant hypohalite ion can be addeddirectly to an aqueous solution or can be generated in situ such as forexample by repeated additions of small amounts of the desired halogensuch as liquid bromine, chlorine gas or iodine as a solid or solution.Suitable hypohalites which can be added directly include all alkalimetal and alkaline earth hypochlorites, hypobromites, hypoiodites.Examples of suitable hypohalite compounds include Ca(OCl) Ca(OBr) KOCl,KOBr, NaOCl, and NaOBr. It is preferred that the hypohalite ions begenerated in situ for reasons stated hereinafter.

Generally, the solubility of the methylenediphosphonate, malonate and/orphosphonoacetate in the aqueous hypohalite solution can be substantiallycontrolled, i.e., increased or decreased, by increasing or decreasingthe organic water-miscible solvent concentration, respectively. Thegreater the solvent concentration in the aqueous solution, the higherthe solubility of the methylenediphosphonate, malonate andphosphonoacetate reactants in the aqueous solution. The reverse is alsotrue, that is, the lower the water-miscible solvent concentration thelower the solubility of these reactants. The solubility of themethylenediphosphonates, malonates and/or phosphonoacetates in theaqueous reaction solution can also be increased or decreased byincreasing or decreasing the temperature, respectively.

Generally, whether the reaction product is the monohalo or dihaloderivative of the methylenediphosphonates, malonates ordiphosphonoacetates is controlled by the proportion of the hypohalitereactant employed. If the desired end product is the monohalogenatedderivative, from about 0.75 to about 1.1 moles of hypohalite ion per 1mole of methylenediphosphonate or phosphonoacetate, should be used. Formaximum yields of the monohalide it is preferred that from about 0.95 toabout 1.1 moles of hypohalite ion per mole of methylenediphosphonate,malonate or phosphonoacetate be employed. Amounts of hypohalite greaterthan about 1.1 moles per mole of methylenediphosphonate, malonate orphosphonoacetate tend to favor the formation of increasing amounts ofdihalogenated product.

Recovery of the halogenated methylenediphosphonate, malonate andphosphonoacetate products from the reaction mixture can be performed byextraction with a waterimmiscible, organic solvent followed byconventional decanting methods, and either column chromatography,selective extraction, distillation or fractional crystallization.

At extreme conditions, e.g., 6 moles of hypohalite per mole ofmethylenediphosphonate, malonate, or phosphonoacetate reactant and 75C., the alkenyl esters can react further with the hypohalite to formhalohydrins. Therefore, in general, these extreme conditions should beavoided when alkenyl esters are used.

In practicing each of the foregoing embodiments of this invention caremust be taken that the reaction temperatures are not so high that thehypohalite ion (OX'" is converted to the halate ion (O X creating adeficiency of hypohalite ion in the reaction mixture. For ex-- ample,temperatures up to about 50 C. are usually satisfactory for theavoidance of hypochlorite conversion, but are only marginallysatisfactory for hypobromite conversion avoidance. Mowever, bygenerating the hypohalite in situ the reactions can be conducted atsubstantially higher temperatures, i.e., over 80 C., as the hypohaliteion reacts with the methylenediphosphonate, malonate or phosphonoacetatebefore there is time for it to disproportionate to form halate ion.

The temperature must not be so high that it reaches a point at whichundesirable ester saponification becomes significant. The temperature atwhich saponification occurs is governed by the pH of the system that isbeing used, higher pH favoring more saponification. Ester saponificationto a significantly detrimental degree will occur above about 75 C. whenthe pH of the system is near neutrality, i.e., from about pH 7 to aboutpH 9. However, at highly basic pHs saponification will occur to adetrimental degree at lower temperatures.

Care must be taken to avoid excessive formation of hypohalous acid inthe reaction system. The aqueous reac tion medium must be kept basicenough to sustain the desired hypohalite ion. If the pH of the reactionsystem drops below about 7 the equilibrium HOX- ,--OX +H+ will shift tothe left, causing the hypohalite ion to disappear. Consequently, the pHof the reaction system must be kept above about 7 in the case ofchlorine addition, and should be above about a pH of 8 for bromineaddition and above a pH of 10 for iodine addition. The reaction for eachhalogen can be conducted with a pH as high as about 14 and it ispreferable that the pH of the reaction solution be above about 11.

The tetraalkyl methylenediphosphonates used as starting materials inthis invention can be prepared by reacting dibromomethane with atrialkyl phosphite in accordance with the following equation:

wherein R is an alkyl radical as set forth hereinbefore. The trialkylphosphite in this reaction can be derived from a primary alcohol andphosphorus trichloride. The dibromomethane is a high temperaturereaction product of methane and bromine. A more detailed discussion ofthe foregoing appears in U.S. Pat. 3,251,907 of Clarence H. Roy, issuedMay 17, 1966. Trialkyl phosphonoacetates can be prepared as follows:

or they can be purchased commercially. Malonate esters are availablecommercially.

The compounds of this invention are selected from the group consistingof:

(a) Methylenediphosphonates having the formula:

wherein each R is selected from the group consisting of alkyl, aryl,alkaryl, aralkyl, haloalkyl, haloaryl, haloalkaryl, haloaralkyl,alkenyl, haloalkenyl, and nitroaryl radicals containing from 9 to about22 carbon atoms, one X is selected from the group consisting ofchlorine, bromine and iodine atoms and the other X is selected from thegroup consisting of chlorine, bromine, iodine and hydrogen atoms;

(b) Malonates having the formula:

R OOCCX COOR wherein each R is selected from the group consisting ofalkyl, alkenyl, aralkyl, aryl alkaryl, haloal kyl, haloalkenyl,haloaryl, haloalkaryl, haloaralkyl and nitroaryl radicals containingfrom 4 to about 22 carbon atoms, one X is selected from the groupconsisting of chlorine, bromine, and iodine atoms, and the other X isselected from the group consisting of chlorine, bromine, iodine andhydrogen atoms; and

(c) Phosphonoacetates having the formula wherein each 'R is selectedfrom the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl,haloalkyl, haloalkenyl, haloaryl, haloalkaryl, haloaralkyl and nitroarylradicals containing from 8 to about 22 carbon atoms, one X is selectedfrom the group consisting of chlorine, bromine and iodine atoms and theother X is selected from the group consisting of chlorine, bromine,iodine and hydrogen atoms.

These compounds are all extreme pressure additives when used at aboutthe 5% level in an SAE 20 mineral oil. All of these compounds whichcontain alkyl groups having seven or more carbon atoms are also antiwearadditives for lubricants when used as set forth hereinbefore. The use ofthese additives in lubricant compositions is more fully discussed in thecopending application of Robert 'Earl Wann, Denzel Allan 'Nicholson andTed Joe Logan, Ser. No. 762,966, filed Sept. 26, 1968, entitled,Lubricant Composition, which is now U.S. Pat. 3,579,449. Thisapplication is incorporated herein by reference.

EXAMPLE I Preparation of tetraheptyl dichloromethylenediphosphonate Al-mole batch of tetraheptyl dichloromethylenediphosphonate is preparedby the following reaction:

2 moles of NaOCl (2840 cc.s of a commercially available product of 5.25%NaOCl in H O) are placed in a 7 3-liter flask and cooled to 10 C. Onemole (568 grams) of tetraheptyl methylenediphosphonate is then addedrapidly. One hundred cc.s of methanol are added to increase solubilityof the tetraheptyl methylenediphosphonate in the H 0. After exothermicactivity has ceased, about 15 minutes, the solution is extracted withCHCl three times. The combined CHCl layers are dried over anhydroussodium sulfate for fifteen minutes, then filtered and evaporated down tothe oily product. This product can be further purified by heating to -lOC. in a 50;]. pressure system. This yields a substantially pure product,tetraheptyl dichloromethylenediphosphonate, in '80%- 95% yield.

EXAMPLE 11 Preparation of tetrakis(decyl)dibromomethylenediphosphonate Aone-mole batch of tetrakis(decyl) dibromomethylene diphosphonate isprepared by a fairly simple two-step reaction:

Step No. 1.--A three-liter reaction flask is charged with 1000 cc. of awater solution of 4 moles (1-60 grams) of NaOH and this solution iscooled to 05 C. Two moles (3200 grams) of Br are then added rapidly,with careful temperature control, to produce NaOBr along with NaBr and H0 in equimolar amounts which have no etfect on the second step of thereaction. The reaction is now ready to proceed with Step No. 2.

Step No. 2.- One mole (736.0 grams) of tetrakis- (decyl)methylenediphosphonate is then added rapidly with careful attention totemperature changes. When all the tetrakis(decyl) methylenediphosphonatehas been added and the reaction shows no signs of any exothermicactivity or is very slowly exothermic, 100 cc.s of methanol are added toincrease solubility of the tetrakis(decyl) methylenediphosphonate in theH 0 containing the NaOBr. The temperature is controlled carefully atthis point (-10 C.). The reaction mixture is stirred until no moreexothermic activity is evident and the color of the solution has gonefrom a reddish-brown (the color of the mixture after Step No. 1.) to alight yellow or white color. At this point the H 0 layer is extractedthree times with CCl The combined CCL; layers are dried over anhydroussodium sulfate for fifteen minutes, then filtered and the CC];evaporated off, leaving a clear, colorless oil which is further purifiedby heating to -100 C. in a 50a pressure system. This yields asubstantially pure product, tetrakis(decyl)dibromomethylenediphosphonate, in a 75- 90% yield.

EXAMPLE III Preparation of tetrabehenyl diiodomethylenediphosphonate Al-mole batch of tetrabehenyl diiodomethylenediphosphonate ester can beprepared by the following reaction:

Two moles (506 grams) of I are placed in a 3-liter flask along with 4moles of NaOH and 2 moles (332.0 grams) KI in 1 liter H 0 and cooled toC. 1 mole (1411 grams) of tetrabehenyl methylenediphosphonate is thenadded rapidly. Two hundred cc.s of methanol are added to increase thesolubility of the tetrabehenyl methylenediphosphonate in the H 0. Moremethanol is used, if necessary, to cause reaction. After the exothermicactivity has ceased, the solution is extracted with CHCl three times.The combined CHCl layers are dried over anhydrous sodium sulfate forfifteen minutes, then filtered and evaporated down. The product is darkin color. After all CHCl is removed by mild heating and exposure to a50;. vaccum the product, tetrabehenyl diiodomethylenediphosphonate, isfound to be substantially pure in 70%90% yields.

EXAMPLE IV Preparation of dipentyl dichloromalonate A l-mole batch ofdipentyl dichloromalonate is prepared by the following reaction:

Two moles of NaOCl (2840 cc.s of a commercially available product at5.25% NaOCl in H O) are placed in a 3-liter flask and cooled to 0 C.(500 cc.s CCl added). One mole (244.0 grams) of diphentyl malonate isthen added rapidly in methanol solution. The solutions are stirredvigorously for 15 minutes at which time they are separated and the CCL;layer dried over anhydrous sodium sulfate, filtered, and evaporateddown. A 50% yield of dipentyl dibromomalonate is obtained fairly easily;however, if methanol is used in the pot during or immediately followingaddition of the dipentyl malonate, yield is boosted to 90%.

EXAMPLE V Preparation of bis(dodecyl)dibrornomalonate A l-mole batch ofbis(dodecyl) dibromomalonate is prepared by the following reaction:

Four moles of NaOH are dissolved in 1 liter of H 0 in a 3-liter flaskand the solution is cooled to 0 C. One mole of bis(dodecyl) malonate isadded carefully and 100 cc.s of methanol are added to insure solubility,The two phase system is then stirred vigorously as 2 moles of Br aredripped in at a reasonably fast rate (as fast as will allow temperaturecontrol at O5 C.). After all the bromine has been added, the solution isstirred for ten minutes more, then the two layers are separated. Afterextraction 3 times with CCl the CCl layer is dried over anhydrous sodiumsulfate, then filtered and evaporated down. The product is furtherpurified by heating in a vacuum of -100n. This yields a substantiallypure material, bis(dodecyl) dibromomalonate, in -90% yields.

EXAMPLE VI Preparation of bis(stearyl) diiodomalonate EXAMPLE VIIPreparation of trioctyl dichlorophosphonoacetate A l-mole batch oftrioctyl dichlorophosphonoacetate is prepared by bubbling 2 moles C1(142.0 grams) into a flask containing 1 mole (476 grams) of trioctylphosphonoacetate in CCL, solution, and 4 moles NaOH (160.0

grams) in H O solution at 0 C. After the C1 has been added 100 cc.sacetone are added to increase solubility of the trioctylphosphonoacetate in the hypochlorite-containing H O layer. Someexothermic activity is noticed and the reaction temperature is kept at 5C. by external cooling. After 15 minutes of vigorous stirring, thelayers are separated. The CCl layer is dried over anhydrous sodiumsulfate for several minutes, then filtered and the solvent removed byevaporation. The product, trioctyl dichlorophosphonoacetate, is asubstantially pure product in -99% yields.

EXAMPLE VIII Preparation of tris(pentadecyl)dibromophosphonoacetate Al-mole batch of tris(pentadccyl) dibromophosphonoacetate is prepared bydripping 2 moles Br (320.0 grams) into a flask containing 1 mole (775.5grams) of his- (pentadecyl) dibromophosphonoacetate in CCl, solution,and 4 moles NaOH (166.0 grams) in H O solution at C. After the Br hasbeen added 100 cc.s tetrahydrofuran are added to increase solubility ofthe tris(pentadecyl) phosphonoacetate in the hypobromite-containing H Olayer. After the exothermic activity has ceased (temperature is heldfrom 05 C.), about minutes, the layers are separated. The C01 layer isdried over anhydrous sodium sulfate for several minutes, then filteredand the solvent removed by evaporation. The product is a substantiallypure material, tris(pentadecyl) dibromophosphonoacetate, in 80-90%yields.

EXAMPLE IX Preparation of tris(eicosyl) diiodophosphonoacetate A l-molebatch of tris(eicosyl) diiodophosphonoace tate is prepared by drippingtwo moles I (506.0 grams) in CCL, solution into a flask containing 1mole (980.0 grams) of tris(eicosyl) phosphonoacetate in CCL, solution,and 4 moles (160.0 grams) NaOH in H O solution at 0 C. After the 1 hasbeen added, 300 cc.s ethanol are added to increase solubility of thetris(eicosyl) phosphonoacetate in the hypoiodite containing H O layer.After the exothermic activity has ceased, during which time thetemperature is held at 0 C. in an ice bath, the layers are separated andthe CCL, layer dried over anhydrous sodium sulfate for 15 minutes, thenfiltered and the CCl removed by evaporation. The product, tris(eicosyl)diiodophosphonoacetate, is a substantially pure material and is obtainedin 7090% yields.

EXAMPLE X One mole of the material in column (A) is reacted withsufficient amounts of the material in column (B) to In general, thedihalo methylenediphosphonates, malonates and phosphonacetates arebetter extreme pressure additives than the monohalomethylenediphosphonates, malonates and phosphonoacetates. Also, ingeneral, the diiodo substituted methylenediphosphonates and malonatesare better than the dibromo substituted methylenediphosphonates andmalonates which, in turn, are better than the dichloro substitutedmethylenediphosphonates and malonates as extreme pressure additives forlubricants. The dichloro, dibromo, and diiodo phosphonoacetates are moreequivalent as extreme pressure additives for lubricants. With theexception of the malonates which contain alkyl groups having less thanseven carbon atoms, all of the compounds of this invention are valuablein that they have antivvear properties as well as extreme pressureactivity when used in lubricant compositions. Suitable lubricantcompositions include those Where of any of the above specifically namedcompounds prepared in Examples I-X are used in an SAE 20 mineral oil.

Preferred compounds for extreme-pressure activity include the dibromoanddiiodomalonates containing R groups having from four to about sevencarbon atoms. Dibromo and diiodo malonates containing R groups having atleast four carbon atoms are surprisingly less corrosive than dibromo anddiiodo malonates containing R groups having less than four carbon atoms.

When, in the above Examples I-X, the following water miscible organicsolvents are substituted, either wholly or in part (e.g., a 1:1 ratio byweight) for the methanol, substantially equivalent results are obtainedin that good yields of the desired products are obtained: ethanol,propanol, ispropanol, butanol, isobutanol, glycerine, ethylene glycol,propylene glycol, ethylene glycol diethyl ether, diethylene glycoln-butyl ether, ethyene glycol n-butyl ether, propylene glycol butoxyether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether,acetone, propyl methyl ketone and/or methyl ethyl ketone.

provide 2.1 moles of the hypohalite ion produced by the material inColumn (B) using the procedure of Example III, to give the product inColumn (C).

Tetra(Z-ethylhexyl)methylenediphosphonate OE(OBI)2Tetra(dodeeenyDmethylenediphcsphonate. KOI Tetranaphthylmethylenediphosphonate K001 Tetrabenzyl meth lenediphosphonate KOBrTetra(octylphenyl methylenediphosphonate Ba(0 01);;Tetra(diehlorostearyl) methylenediphosphonate Ca(00h)Tetra(6,9-di.fluorononadecenyl) methylenediphosphonate NaOOlTetra(2-bromonaphthyl) methylenediphosphonate NaOBrTetra(2,4-diiodobenzyl) methylenediphosphonate NaOITetra(2-ch1oroethy1pheny1) methylenediphosphonate NaOGlTetra(4-nitronaphthyl) methylenediphosphonate Ca(OI)z Di(2-ethy1hexyl)malonate KOBr Do KOI Di (octadecenyl) malonate KOBr Dinaphthyl "malnnatnNaOI Dibenzyl malonate NaOBr Di(pentadecy1phenyl) malonate Oa(0Br)aDi(tetrachlorostearyl) malonate-.- Ca(OCl)z Di(5-iodopentadecyl)malonate--. OI Di(6-ch1oronaphthy1) malonate Ca(OI)2Di[6-(1,3-dich1oropheny1) decy1]ma1onate... NaOBr Di(2,3-dibrmodeeylphenyl)malonate-.-.. NaOBr Di (4,6-dinitronaphthyl)malonate N aOITri(2-ethylhexy1)phosphonaocetate- NaOCl Tri(oetenyl)phosphonoacetateNaOI Trinaphthyl phosphonoacetate- KOBt 'lribenzyl phosphonoacetate OITn(dodeeylphenyl)phosphonoacetate. Ca(O CD1Tri(9,10-di.iodostearly)phosphonoacetate aOITri(3-bromoeicosenyl)phosphonoacetate NaOOl Tri(6-chloronaphthyl)phosphonoaeetate K001 Tri(2-bromo-6-phenyldeeyl)phosphonoacetate.- KOITn(Zchlorodeeylphenyl)phosphonoacetate N a0 ClTn(4-nitronaphthenyl)phosphonoacetate NaOBr 2-ethylhexyl stearylmalonate NaOI Tetra(2-ethylhexyl)dibromomethylenediphosphonate.Tetra(dodeceuyl) diiodomethylenediphosphonate. Tetranaphthyldichloromethylenediphosphonate. Tetrabenzyld1bromomethylenediphosphonare. Tetra(octylphenyl)dichloromethylenediphosphonate. Tetfia(ditchlorostearyl)diehloromethyleuediphosp ona e. Tetra(6,9-clifluorononadecenyl)dichloromehtylenediyhosphonate. Tetfiafl-ilsiromonaphthyl)dibromomethylenediphosp ona e. Tetra(2,4-diiodobenzyl)methylenediphosphonate. Tetra(2-eh1oroethylphenyl)dichloromethylenediphosphonate. TetraG-nitronaphthyl)diiodomethylenediphospho- When, in the above Examples I-X, 1.05 moles ofhypohalite ion per mole of methylenediphosphonate, malonate, orphosphonoacetate reactant are used instead of the indicated amounts, andthe hypohalite is added last and dropwise to the reaction mixture whichis being vigorously stirred, the products are the correspondingmonobromo, monochloro and monoiodo methylenediphosphonates, malonatesand phosphonoacetates.

What is claimed is:

1. A process for preparing halogenated, malonate esters comprising thesteps of reacting a compound selected from the group consisting ofmalonates having the formula ROOCCH COOR' wherein each R is selectedfrom the group consisting of alkyl, alkenyl, aryl, aralkyl, alkaryl,haloalkyl, haloalkenyl, haloaryl, haloalkaryl, haloaralkyl, andnitroaryl radicals containing from 4 to about 1 1 22 carbon atoms with ahypohalite ion selected from the group consisting of OCl-, OBF, and 01-,the molar proportions of the reactant being selected so that there arefrom about 0.75 to about 6 moles of said hypohalite ion for each mole ofsaid malonates, in a two-phase reaction mixture comprised of (A) anaqueous solution con taining essentially no added electrolyte and from1% to about 50% by weight of a water miscible organic solvent, and (B)an organic phase comprising said malonates, the temperature of thereaction being in the range of from 0 C. to 75 C. the pH of the aqueoussolution being greater than about 7 and the reaction time being fromabout 1 minute to about 2.0 hours.

2. The process of claim 1 wherein the malonate and the hypohalite ionare present in a molar ratio of from about 1:0.75 to about 111.1malonatechypohalite.

3. The process of claim 2 wherein the molar ratio is from about 1:0.95to 1:1.1 malonatezhypohalite.

4. The process of claim 1 wherein the malonate and the hypohalite ionare present in a molar ratio of from about 1:2 to about 1:6 malonate:hypohalite.

5. The process of claim 4 wherein the molar ratio is from about 1:2.05to about 1:2.1 mal0nate:hypohalite.

6. The process of claim 1 wherein each R is an alkyl group.

7. The process of claim 1 wherein the water miscible organic solvent isselected from the group consisting of (a) alcohols containing from 1 to3 hydroxy groups and from 1 to 6 carbon atoms. (1)) ethers containingfrom 2 to about 8 carbon atoms, and (c) ketones containing from 3 toabout 5 carbon atoms.

8. The process of claim 1 wherein the water miscible solvent is selectedfrom the group consisting of methanol, ethanol, propanol, isopropanol,butanol, isobutanol, glycerine, ethylene glycol, propylene glycol,ethylene glycol diethyl ether, diethylene glycol n-butyl ether, ethyleneglycol n-butyl ether, propylene glycol butoxy ether, propylene glycolisobutoxy ether, dipropylene glycol butoxy ether, tetrahydrofuran,1,4-dioxane, ethylene glycol dimethyl ether, acetone, propyl methylketone, and methyl ethyl ketone.

References Cited UNITED STATES PATENTS 3,579,449 5/1971 Wann et al.260590 OTHER REFERENCES Beilstein, Handbuch der Org. Chem. Band II, 3rdsupp, pp. 1639-1641 (1961).

Bondarchuk et al., C. A. 63, p. 5549 (1965).

LORRAINE A. WEINBERGER, Primary Examiner E. J. SKELLY, AssistantExaminer US. Cl. U.S. 260479 S

